4-Benzyloxymethyl-4-alkyl-2-alkyl-1,3-dioxolane-2(N-thiazolyl) carboxamides

ABSTRACT

New compounds of the formula   wherein R1 and R2 each is alkyl; R3 is a nitrogen-containing heterocyclic group; and R4 is optionally substituted phenyl, are useful as herbicides.

United States Patent [191 Isaac et al.

[ Nov. 18, 1975 4-BENZYLOXYMETHYL-4-ALKYL-2- ALKYL-l,3-DIOXOLANE-2(N-THIAZOLYL) CARBOXAMIDES [75] Inventors: Eirlys R. Isaac, Sittingbourne; Peter Kirby, Maidstone, both of England [73] Assignee: Shell Oil Company, Houston, Tex.

[22] Filed: June 25, 1974 [21] Appl. No.: 482,935

[30] Foreign Application Priority Data July 3, l973 United Kingdom 31604/73 [52] US. Cl 260/3063 R; 71/90; 71/94;

260/295 AM; 260/3068 D [51] Int. Cl? C07D 405/12; C07D 417/12 [58] Field of Search 260/3068 R [56] References Cited UNITED STATES PATENTS 3,427,318 2/1969 Barber et al. 260/3068 R 3,496,187 2/1970 Bruderlein et al. 260/3068 R X OTHER PUBLICATIONS Kirby et al,; Chemical Abstracts, Vol. 78 (1973). 721l2w.

Primary ExaminerRichard L. Raymond [57] ABSTRACT New compounds of the formula 3 Claims, N0 Drawings 4-BENZYLOXYMETtl-YL e-A-LKYLeZ- ALKYL-T,3-

DIOXOLANE-MN Tl-llAZoLYL.) CARBOXAMIDE S.

wherein R, and R each' 'repres'ents an alkyl group; R represents a nitrogen-containing heterocyclic group; and R, represents a'phenyl g'r'oup optionally substituted y l or b a y I More particularly, the invention is directed to amide derivatives of general formula [wherein R, and each represents an alkyl group of 1-6 carbon atoms; R rep,- resents a 5- or 6-membered heterocyclic group containing l to 2 nitrogen atoms in the ring and to 1 sulfur atoms in the ring; and R represents a phenyl group optionally substituted by fluorine or chlorine or by an alkyl group of 1-6 carbon atoms.

Because of their properties, preferred amide derivatives are those of formula I wherein R and R each represents an alkyl group of 1-6 carbon atoms, for example methyl, ethyl, or propyl; R represents a 5- to 6- membered nitrogen-containing heterocyclic group, for example, thiazolyl, thiadiazolyl or pyridyl, and R represents a phenyl group optionally substituted by one or two chlorine atoms or by an alkyl group of 1-6 carbon atoms, for example by methyl. 7 I

The compounds of formula I may be prepared by a process which comprisesreac ting a compound of formula:

mocl-ua,

wherein R represents an alkyl group, with an amine of the formula: e i

V .NHzRa When R is an alkyl group the reaction is suitably carried out in the' presence of a strong base, for example an alkali metal hydride such as sodium hydride The compounds of formula "wherein R5 is alkyl are known compounds, disclose in Netherlands Pat. No. 72,07026. I

As mentioned above the amide derivatives of the invention are of interest as herbicides, and the invention includes, therefore, herbicidal compositions comprising a carrier and/or a surface active agent, together with, as active ingredient, an amide derivativeof the invention. Likewise the invention also includes a method of combating weeds at a locus which comprises applying to the locus an amide derivative or composition of the invention.

. compound is mixed or formulated to facilitate its application to the plant, seed, soil or other object to be treated, or its storage, transport or handling.

The surface-active agent may be an emulsifying agent or a dispersing agent or'a wetting agent; it may be nonionic or ionic.

'Any of the carrier materials or surface-active agents I usually applied in formulating pesticides may be used in the composition of the invention, and suitable examples of these are to-be found, for example, in UK specification Noi 1,232,930.

The" compositions of the'invention may be formulated aswettable powders, dusts, granules, solutions, e'mulsifiable concentrates, emulsions, suspension concentrates or aerosols. wettable powders are usually compounded to contain 25, 50 or 75% w of toxicant and usually contain, in addition to solid carrier, 3-l0% vw of a dispersing agent and,where necessary, 0-] 0% w of stabil izer(s) and/or other additives such as penetrants or stickers.Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and are diluted in the field with,fu rther solid carrier to give a composition usually containing Ii-10% .w of toxicant. Granules are usually prepared to have a size between l0 and 100 BS mesh (l.676-0.l52 mm), and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain 12-25% w active ingredient and 0-l0% w of additives such as stabilizers, slow release modifiers and binding agents. Emultrates are compounded so as to obtain a stable, non- The term carrier" as used herein means a solid or sedimenting, flowable product and usually contain 10-75% w active ingredient, 05-15% w of .dispersing agents, 0.1-:l 0% w of suspending agents such as protective colloids 'and thixotropic agents, 0-l0% w of appropriate' additives such as defoamers,'corrosion inhibitors, stabilizers, penetra'nts and stickers, and as carrier, water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be dissolved in the carrier to assist in preventing sedimentation or as antifreeze agents for wate'n' I Aqueous dispersions and emulsions, for example, compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also liewithin the scope of the present invention. The said emulsions may be of the water-in-oil or of the oilin-water type, and may have a thick mayonnaise-like consistency.

The compositions of the invention may also contain other ingredients, for example, other compounds possessing pesticidal, especially insecticidal, acaricidal, herbicidal or fungicidal properties.

The lnvetltitjrl 'is further illustrated in the following examples. It should be understood, however, that the examples are'for the purpose of illustration only and should not be regarded as limiting the invention in any way.-ln the examples the structure of the compounds was confirmed by elemental analysis and NMR spectral analysis. i I '1 i were stirred together in dimethyl sulphoxide (50ml) for l 16 hours at room temperature. The reaction mixture was poured onto ice and extracted with chloroform. The organic solution was washed twice with water, dried and the solvent evaporated. The residue was purified (chromatography on silica gel using chloroform as eluant) to give desired product 3.lg (33%) as an oil.

Analysis: Calculated for C H N O C,67.4; H,6.8; N,7.9%. Found C,67.4; H, 7.1; N,7.8%

EXAMPLES 2-5 Following procedures similar to those given in the previous Example further compounds were prepared, for which physical characteristics are given in the following Table I.

TABLE 1 4 drenched with a liquid formulation containing a compound of the invention, and in the foliar spray tests the seedling plants were sprayed with such a formulation.

The soil used in the tests was a steam-sterilized, modified John lnnes Compost mixture in which half the peat, by loose bulk, had been replaced by vermiculite.

The formulations used in the tests were prepared by diluting with water solutions of the compounds in acetone containing 0.4% by weight of an alkylphenol/ethylene oxide condensate available under the trade name Triton X-l 55. In the soil spray and foliar spray tests the acetone solutions were diluted with an equal volume of water and the resulting formulations applied at two dosage levels corresponding to 10 and l kilograms of active material per hectare respectively in a volume equivalent to 400 liters per hectare. In the soil drench tests one volume of the acetone solution was diluted to 155 volumes with water and the resulting formulation applied at one dosage level equivalent to kilograms of active material per hectare in a volume equivalent to approximately 3,000 liters per hectare.

The herbicidal effects of the compounds were as.- sessed visually seven days after spraying the foliage and Compound or refractive index 2. 4-benzyloxymethyl-4-ethyl-2-methyl-l,3-dioxo- Ian-Z-(N-thiazol-Z-yl)carboxamide n I.52l0 3. 4-benzyloxymethyl-2.4-dimethyl-l,3-dioxolan- -2-(N-pyrid-4-yl)carboxamide n l.5l05 4. 4-benzyloxymethyl-4-ethyl-2-methyl-l.3-dioxolan-2-(N-S-methyl-thiadiazol-Z-yl)carboxamide isomerA 5. 4-benzyloxymethyl-4-ethyl-2-methyl-l.3-dioxom.p.

lan-2-( N-5-methyl-thiadiazol-2-yl )carboxamide l37-l40 EXAMPLE 6 Herbicidal Activity To evaluate their herbicidal activity, compounds of the invention were tested using as a representative range of plants: maize, Zea mays (M2); rice, oryza sativa (R); barnyard grass, Echinchloa crusgalli (BG);

TABLE 2 Post-Emergence Pre-emergence Dosage Example kglha Soil Drench Foliar Spray Soil Spray MzR PLMSBMzR PLMSBMzR PLMSB G G G l 10 7 6 8 5 8 3 5 7 4 8 5 7 5 5 9 9 9 9 7 7 7 l 2 0 7 S 6 0 5 8 9 9 9 7 3 3 2 l0 7 5 7 4 7 3 6 7 4 8 5 7 2 5 9 9 9 9 7 6 7 I O 0 7 4 7 0 5 8 9 9 8 7 5 3 3 10 7 3 7 0 0 0 3 3 4 8 7 8 8 4 9 9 9 8 7 7. 5 l 0 0 I 2 I 2 2 0 6 8 0 0 0 0 pea, Pisum sativum (P); linseed, Linum usitatissium (L); mustard, Sinapis al ba (M); and sugar beet, Beta vulgaris (SB).

The tests fall into two categories, pre-emergence and We claim as our invention: 1. An amide derivative of the formula wherein R, and R each represents an alkyl group of 1-6 carbon atoms, R represents thiazolyl; and R represents a phenyl group optionally substituted by fluo- 6 rine or chlorine or by an alkyl group of 1-6 carbon carbon atomstoms 3. 4-benzyloxymethyl-4-ethyl-2-methyl-l ,3-dioxolana 2-(N-thiazol-Z-yl)carboxamide.

2. An amide derivative according to claim 1 wherein R represents a phenyl group optionally substituted by 5 one or two chlorine atoms or by an alkyl group of l-6 

1. AN AMIDE DERIVATIVE OF THE FORMULA
 2. An amide derivative according to claim 1 wherein R4 represents a phenyl group optionally substituted by one or two chlorine atoms or by an alkyl group of 1-6 carbon atoms.
 3. 4-benzyloxymethyl-4-ethyl-2-methyl-1,3-dioxolan-2-(N-thiazol-2 -yl)carboxamide. 